Sequential Double Claisen Rearrangement and Two-Directional Ring-Closing Metathesis as a Route to Various Benzofused Bisoxepin and Bisoxocin Derivatives

Shital K. Chattopadhyay; Titas Biswas; Susama Maity

doi:10.1055/s-2006-950398

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Synlett 2006(14): 2211-2214
DOI: 10.1055/s-2006-950398

LETTER

Sequential Double Claisen Rearrangement and Two-Directional Ring-Closing Metathesis as a Route to Various Benzofused Bisoxepin and Bisoxocin Derivatives

Shital K. Chattopadhyay*, Titas Biswas, Susama Maity
Department of Chemistry, University of Kalyani, Kalyani - 741235, India
Fax: skchatto@yahoo.com; e-Mail: +91(33)25828282;

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Publication History

Received 14 February 2006
Publication Date:
24 August 2006 (online)

Abstract
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Abstract

A synthetic strategy based on tandem application of double Claisen rearrangement and two-directional ring-closing metathesis reaction as key-steps has been developed for the synthesis of various hitherto unknown tri-, tetra- and pentacyclic benzofused bisoxepin and bisoxocin derivatives.

Key words

Claisen rearrangement - ring-closing metathesis - oxepine - oxocine

References and Notes

1 Stefinovic M. Snieckus V. J. Org. Chem. 1998, 63: 2808

Crossref Search in Google Scholar
2a Kishuku H. Shindo M. Shishido K. Chem. Commun. 2003, 350

Crossref
2b Sabui SK. Venkateswaran RV. Tetrahedron Lett. 2004, 45: 983

Crossref Search in Google Scholar
2c Lecornue F. Ollivier J. Synlett 2004, 1613

Crossref
2d Vyvyan JR. Oaksmith JM. Parks BW. Peterson EM. Tetrahedron Lett. 2005, 46: 2457

Crossref Search in Google Scholar
3 Huang S. Kuo H. Chen C. Tetrahedron Lett. 2001, 42: 7473

Crossref Search in Google Scholar
4 Satoh Y. Libby AH. Powers C. Kowalski T. White DH. Kimble EF. Bioorg. Med. Chem. Lett. 1994, 4: 549

Crossref Search in Google Scholar
5 Kiyama R. Honma T. Hayashi K. Ogawa M. Hara M. Fujimoto M. Fujishita T. J. Med. Chem. 1995, 38: 2728

Crossref Search in Google Scholar
6 Carl K, and Joseph L. inventors; US 4,073,912; Chem. Abstr. . 1978, 89, 24156
7 For a review, see: Yet L. Chem. Rev. 2000, 100: 2963

Search in Google Scholar
For some recent applications of RCM reaction in medium ring heterocycle formation, see:
8a Barberis M. Losada PG. Pleite S. Rodriguez JR. Soriano JF. Mendiola J. Tetrahedron Lett. 2005, 46: 4847

Thieme Connect Search in Google Scholar
8b Gracias V. Gasiecki AF. Djuric SW. Org. Lett. 2005, 7: 3183

Thieme Connect Search in Google Scholar
8c Kim YJ. Lee D. Org. Lett. 2004, 6: 4351

Thieme Connect Search in Google Scholar
8d Lane C. Snieckus V. Synlett 2000, 1294

Thieme Connect
9a Chattopadhyay SK. Maity S. Panja S. Tetrahedron Lett. 2002, 43: 7781

Thieme Connect Search in Google Scholar
9b Chattopadhyay SK. Dey R. Biswas S. Synthesis 2005, 403

Thieme Connect
10 Kotha S. Mandal K. Tetrahedron Lett. 2004, 45: 1391

Crossref Search in Google Scholar
11 Pain C. Celanire S. Guillaunet G. Joseph B. Synlett 2003, 2089

Thieme Connect
12a Wallace DJ. Tetrahedron Lett. 2005, 46: 591

Thieme Connect Search in Google Scholar
12b Clark JS. Hamelin O. Angew. Chem. Int. Ed. 2000, 39: 372

Thieme Connect Search in Google Scholar
12c Bassindale MJ. Hamley P. Leituer A. Harrity JPA. Tetrahedron Lett. 1999, 40: 3247

Thieme Connect Search in Google Scholar
12d Fang Z. Hong JH. Org. Lett. 2004, 6: 993

Thieme Connect Search in Google Scholar
12e Ahmed A. Ohler E. Mulzer J. Synthesis 2001, 2007

Thieme Connect
13 Chattopadhyay SK. Paul BK. Maity S. Chem. Lett. 2003, 32: 1190

Crossref Search in Google Scholar
14 Schlosser M. Michel D. Croft SL. Synthesis 1996, 591

Thieme Connect
15a Kong Z.-L. Tzeng S.-C. Liu Y.-C. Bioorg. Med. Chem. Lett. 2005, 15: 163

Crossref Search in Google Scholar
15b Pearson DPG. Leigh SJ. Sutherland IO. J. Chem. Soc., Perkin Trans. 1 1979, 3113

Crossref
15c Sorrell TN. Ellis DJ. J. Org. Chem. 1985, 50: 5765

Crossref Search in Google Scholar
16 Ithart A. Plubrukarn A. Kongsaeree P. Bui T. Keawpradub N. Houghton PJ. Org. Lett. 2003, 5: 2879

Crossref Search in Google Scholar
17 Takahasi I. Nomura A. Kitajama H. Synth. Commun. 1990, 20: 1569

Search in Google Scholar
18 Cambie RC. Howe TA. Pausler MG. Rutledge PS. Woodgate PD. Aust. J. Chem. 1987, 40: 1063

Search in Google Scholar

19

General Procedure for the Synthesis of the Bisdienes.
A heterogeneous mixture of the appropriate biphenol (1.0 mmol), allyl bromide (or 4-bromobutene; 4.0 mmol), anhyd K₂CO₃ (8.0 mmol) and dry acetone (10 mL) was refluxed under stirring under nitrogen atmosphere for 18 h. It was then filtered and the filter cake was washed with acetone (2 × 10 mL). The combined acetone solution was then concentrated in vacuo and the residual mass was chromatographed over silica gel.
Data for compound 3: ¹H NMR (300 MHz, CDCl₃): δ = 6.84 (s, 1 H), 6.13-5.91 (m, 4 H), 5.45 (dd, 2 H, J = 17.1, 1.2 Hz), 5.27 (d, 2 H, J = 9.4 Hz), 5.08 (overlapping doublets, 4 H), 4.28 (d, 4 H, J = 5.4 Hz), 3.36 (d, 4 H, J = 6.5 Hz), 2.22 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 153.9 (s), 137.2 (d), 129.4 (d), 128.7 (d), 125.0 (s), 115.8 (t), 111.4 (s), 75.1 (t), 34.1 (t), 10.7 (q). Anal. Calcd for C₁₉H₂₄O₂: C, 80.24; H, 8.51. Found: C, 80.48; H, 8.39.
Compound 10: ¹H NMR (300 MHz, CDCl₃): δ = 6.67 (s, 2 H), 6.04-5.96 (m, 4 H), 5.42 (dd, 2 H, J = 17.2, 1.4 Hz), 5.22 (dd, 2 H, J = 10.4, 1.1 Hz), 5.04-5.01 (m, 4 H), 4.48 (d, 4 H, J = 1.2 Hz), 3.37 (d, 4 H, J = 6.3 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 150.3 (s), 137.1 (d), 133.8 (d), 127.5 (s), 116.8 (t), 115.4 (t), 114.5 (d), 69.8 (t), 34.2 (t). Anal. Calcd for C₁₈H₂₂O₂: C, 79.96; H, 8.20. Found: C, 80.07; H, 8.23.
Compound 16: mp 82 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.40-7.34 (m, 4 H), 6.88 (d, 2 H, J = 9.1 Hz), 6.15-5.98 (m, 4 H), 5.45 (d, 2 H, J = 17.4 Hz), 5.29 (d, 2 H, J = 9.6 Hz), 5.14-5.05 (m, 4 H), 4.58 (d, 4 H, J = 4.8 Hz), 3.48 (d, 4 H, J = 6.5 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 155.3 (s), 136.9 (d), 133.5 (d), 133.4 (d), 129.0 (s), 128.3 (s), 125.3 (d), 116.8 (t), 115.4 (t), 111.8 (d), 68.8 (t), 34.5 (t).
Compound 28: ¹H NMR (300 MHz, CDCl₃): δ = 7.82 (d, 2 H, J = 8.4 Hz), 7.32 (d, 2 H, J = 8.5 Hz), 6.26-6.15 (m, 2 H), 6.08-5.99 (m, 2 H), 5.51 (dd, 2 H, J = 17.4, 1.4 Hz), 5.32 (dd, 2 H, J = 11.2, 1.0 Hz), 5.13-5.07 (m, 4 H), 4.49 (d, 4 H, J = 5.4 Hz), 3.59 (d, 4 H, J = 6.3 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 152.5 (s), 137.2 (d), 133.9 (d), 128.9 (s), 128.3 (d), 128.0 (s), 118.3 (d), 117.3 (t), 115.9 (t), 75.3 (t), 33.9 (t). Anal. Calcd for C₂₂H₂₄O₂: C, 82.46; H, 7.55. Found: C, 82.57; H, 7.64.
Compound 34: mp 98 °C. IR (KBr,): 1669, 1258, 1073, 993 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 8.04 (d, 2 H, J = 7.9 Hz), 7.60 (d, 2 H, J = 7.9 Hz), 6.27-6.16 (m, 2 H), 6.02-5.94 (m, 2 H), 5.44 (dd, 2 H, J = 17.2, 1.0 Hz), 5.32 (d, 2 H, J = 10.1 Hz), 5.16-5.09 (m, 4 H), 4.54 (d, 4 H, J = 5.6 Hz), 3.55 (d, 4 H, J = 6.4 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 180.5 (s), 156.7 (s), 141.6 (s), 135.7 (d), 135.5 (s), 133.7 (d), 125.3 (s), 123.4 (d), 118.0 (t), 117.0 (t), 75.2 (t), 34.2 (t). Anal. Calcd for C₂₆H₂₄O₄: C, 77.98; H, 6.04. Found: C, 78.11; H, 6.20.

20

General Procedure for TDRCM.
To a solution of the appropriate bisdiene (0.2 mmol) in dry, degassed CH₂Cl₂ (25 mL) was added Grubbs’ catalyst (5, 15 mg, 10 mol%) under argon atmosphere and the resulting solution was stirred at r.t. for the time indicated in Table [1] . The solvent was the removed in vacuo and the residue was chromatographed over silica gel.

21

All new compounds reported here gave satisfactory spectroscopic and/or analytical data.
Compound 6: mp 140-141 °C. ¹H NMR (300 MHz, CDCl₃): δ = 6.65 (s, 1 H), 5.85-5.79 (m, 2 H), 5.43 (d, 2 H, J = 11.5 Hz), 4.53 (s, 4 H), 3.37 (d, 4 H, J = 2.5 Hz), 2.20 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 155.5 (s), 131.5 (s), 127.3 (d), 126.0(d), 125.1 (d), 123.4 (s), 70.0(t), 31.3 (t), 8.9 (q). Anal. Calcd for C₁₅H₁₆O₂: C, 78.92; H, 7.06. Found: C, 79.18; H, 7.21. MS (EI): m/z = 228 [M⁺].
Compound 7: ¹H NMR (300 MHz, CDCl₃): δ = 6.77 (s, 1 H), 5.91-5.84 (m, 2 H), 5.68-5.62 (m, 2 H), 3.95 (t, 4 H, J = 4.7 Hz), 3.32 (d, 4 H, J = 7.0 Hz), 2.44-2.39 (m, 4 H), 2.15 (s, 3 H). ¹³C NMR (75 MHz, CDCl₃): δ = 154.7 (s), 134.0 (d), 133.1 (s), 126.9 (d), 125.9 (d), 125.4 (s), 71.9 (t), 31.4 (t), 28.8 (t), 9.6 (q). Anal. Calcd for C₁₇H₂₀O₂: C, 79.65; H, 7.86. Found: C, 79.78; H, 8.01.
Compound 12: mp 143 °C. ¹H NMR (300 MHz, CDCl₃): δ = 6.79 (s, 2 H), 5.85-5.79 (m, 2 H), 5.45 (td, 2 H, J = 11.4, 1.4 Hz), 4.54 (d, 4 H, J = 2.2 Hz), 3.41 (s, 4 H). ¹³C NMR (75 MHz, CDCl₃): δ = 154.5 (s), 135.0 (s), 127.4 (d), 125.6 (d), 121.6 (d), 71.2 (t), 31.3 (t). MS (EI): m/z = 214 (100).
Compound 13: ¹H NMR (300 MHz, CDCl₃): δ = 6.80 (s, 2 H), 5.98-5.87 (m, 2 H), 5.18-5.01 (m, 2 H), 3.95 (t, 4 H, J = 6.5 Hz), 3.35-3.26 (m, 4 H), 2.54-2.51 (m, 4 H). Anal. Calcd for C₁₆H₁₈O₂: C, 79.31; H, 7.49. Found: C, 79.39; H, 7.52.
Compound 18: mp 104 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.34 (dd, 2 H, J = 8.2, 2.3 Hz), 7.25 (d, 2 H, J = 2.8 Hz), 7.10 (d, 2 H, J = 8.1 Hz), 5.93-5.84 (m, 2 H), 5.52-5.47 (m, 2 H), 4.62-4.60 (m, 4 H), 3.53 (d, 4 H, J = 2.8). ¹³C NMR (75 MHz, CDCl₃): δ = 158.0 (s), 136.7 (s), 136.2 (s), 127.5 (d), 127.3 (d), 126.3 (d), 125.7 (d), 121.7 (d), 71.2 (t), 31.9 (t). MS (EI): m/z = 290 [M⁺]. Anal. Calcd for C₂₀H₁₈O₂: C, 82.73; H, 6.25. Found: C, 82.91; H, 6.44.
Compound 19: mp 80 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.37-7.34 (m, 4 H), 7.05 (d, 2 H, J = 8.4 Hz), 5.94 (td, 2 H, J = 10.9, 6.6 Hz), 5.69-5.60 (m, 2 H), 4.08 (t, 4 H, J = 4.9 Hz), 3.46 (d, 4 H, J = 6.5 Hz), 2.41-2.36 (m, 4 H). ¹³C NMR (75 MHz, CDCl₃): δ = 156.7 (s), 136.2 (s), 135.8 (s), 127.1 (d), 126.9 (d), 125.8 (d), 124.3 (d), 122.0 (d), 72.1 (t), 32.1 (t), 28.4 (t). Anal. Calcd for C₂₂H₂₂O₂: C, 82.99; H, 6.96. Found: C, 82.91; H, 6.64.
Compound 24: ¹H NMR (300 MHz, CDCl₃): δ = 7.19-7.05 (m, 6 H), 5.87-5.80 (m, 2 H), 5.39 (d, 2 H, J = 11.4 Hz), 4.36 (t, 4 H, J = 2.1 Hz), 3.54 (d, 4 H, J = 2.4 Hz). ¹³C NMR (75 MHz, CDCl₃): δ = 155.8 (s), 136.6 (s), 132.0 (s), 129.3 (d), 128.1 (d), 127.5 (d), 125.3 (d), 123.4 (d), 70.4 (t), 31.8 (t). MS (EI): m/z = 290 [M⁺]. Anal. Calcd for C₂₀H₁₈O₂: C, 82.73; H, 6.25. Found: C, 82.84; H, 6.32.
Compound 25: ¹H NMR (300 MHz, CDCl₃): δ = 7.17-7.14 (m, 4 H), 7.05 (d, 2 H, J = 7.4 Hz), 5.94 (td, 2 H, J = 10.9, 6.9 Hz), 5.59 (td, 2 H, J = 10.8, 7.3 Hz), 3.63 (t, 4 H, J = 4.9 Hz), 3.47 (d, 4 H, J = 6.7 Hz), 2.30-2.25 (m, 4 H). HRMS (TOF MS ES⁺): m/z calcd.: 318.1619; found: 318.1628.
Compound 30: ¹H NMR (300 MHz, CDCl₃): δ = 7.85 (d, 2 H, J = 6.3 Hz), 7.23 (d, 2 H, J = 6.4 Hz), 5.93-5.89 (m, 2 H), 5.54 (dquint, 2 H, J = 8.7, 1.0 Hz), 4.70-4.68 (m, 4 H), 3.64-3.62 (m, 4 H). ¹³C NMR (75 MHz, CDCl₃): δ = 153.7 (s), 130.8 (s), 128.4 (s), 127.5 (d), 125.7 (d), 117.0 (d), 70.1 (t), 32.0(t). MS (EI): m/z = 264 [M⁺].
Compound 31: mp 176-178 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.78 (d, 2 H, J = 8.4 Hz), 7.33 (d, 2 H, J = 9.1 Hz), 6.02 (dt, 2 H, J = 10.7, 7.1 Hz), 5.63 (dt, 2 H, J = 10.7, 7.3 Hz), 4.18 (t, 4 H, J = 4.7 Hz), 3.54 (d, 4 H, J = 7.1 Hz), 2.51-2.46 (m, 4 H). ¹³C NMR (75 MHz, CDCl₃): δ = 152.4 (s), 133.6 (d), 132.6 (s), 129.3 (s), 127.6 (d), 127.3 (d), 117.7 (d), 72.6 (t), 31.7 (t), 29.0 (t). Anal. Calcd for C₂₀H₂₀O₂: C, 82.16; H, 6.89. Found: C, 82.33; H, 7.02. MS (EI): m/z = 292 [M⁺].
Compound 35: mp 248-251 °C. ¹H NMR (300 MHz, CDCl₃): δ = 7.97 (d, 2 H, J = 7.9 Hz), 7.48 (d, 2 H, J = 7.8 Hz), 5.88-5.85 (m, 2 H), 5.53 (d, 2 H, J = 11.0 Hz), 4.83 (s, 4 H), 3.58 (s, 4 H). ¹³C NMR (75 MHz, CDCl₃): δ = 183.0 (s), 158.2 (s), 146.4 (s), 135.6 (s), 133.8 (d), 128.3 (d), 126.3 (s), 124.7 (d), 123.9 (d), 71.1 (t), 31.1 (t). Anal. Calcd for C₂₂H₁₆O₄: C, 76.73; H, 4.68. Found: C, 76.94; H, 4.62. MS (TOF MS ES⁺): m/z = 344 [M⁺].